CN108368446B - Wear masking composition for reusable containers and method of use - Google Patents

Abstract

A composition for masking scratches on the surface of a container is provided, the composition comprising a carboxylic acid ester, a surfactant, and a monounsaturated fatty acid. The composition is suitable for masking scratches on reusable containers, such as glass or PET bottles. The composition is suitable for application to a cooled, moist surface that has condensed. Methods for making and applying such scratch masking compositions are also provided.

Description

Wear masking composition for reusable containers and method of use

Cross Reference to Related Applications

This application is a non-provisional application of U.S. application No. 62/265,474 filed on 10.12.2015, which is incorporated herein by reference in its entirety.

Technical Field

The present disclosure provides compositions and methods for masking scratches and abrasion on the surface of a container. In particular, the present invention provides compositions and methods suitable for use in cold and moist containers, including glass and PET reusable containers.

Background

Containers, such as returnable bottles, are disposed of multiple times during manufacture, inspection, filling, shipping, washing, etc. During such handling, the bottles contact various mechanical devices, such as conveyors, detection devices, other containers (e.g., bottles, cans, etc.), and surfaces, such as boxes and shelves. This high contact causes damage to the surface by scratching, breaking, cracking, or other defects. This type of abrasion is particularly evident on dark colored products such as green or brown glass or plastic bottles used in the beverage industry. However, these abrasions were also observed in the colorless bottles.

Each time the container is reused, the container is exposed to a chance of scratching or further scratching of the surface. This occurs in particular on the bottle and scratches or scratches generally occur in the shoulder and bottom areas in the form of rings. Such scuffing or wear is not only purely aesthetically undesirable but it is also undesirable from an economic standpoint, as it can adversely affect a customer's purchasing decision. The consumer may choose not to purchase a product with a highly scratched or aesthetically unpleasing container. Thus, wear may reduce the maximum number of reuses or refills per container.

It is known to use scratch or mar masking agents on glass containers. Such masking agents are desired to mask scratches and exhibit acceptable surface characteristics and durability. Desirably, the scuff masking agent is water resistant, durable, non-toxic, and removable in alkaline bottle washing operations. In addition to these properties, the scuff masking agent exhibits good scuff masking properties, dries well, is non-tacky, remains on the container after washing or alternatively is easily removed during washing, is moisture resistant, and meets food safety requirements. Coating systems that rely on heat curing or dry application of coatings are ineffective on production lines where glass bottles are cool. Heating may not be possible because increasing the temperature of the product to be placed in the container may be detrimental to the organoleptic properties of the product. Even if heating is possible for the product contained in the glass, an additional drying step may not be possible, since the coating process is usually automated. There is substantially no time for a substantial drying step including heating.

The protective coating is applied to the glass container during the manufacture of the hot end process and/or the cold end process. In cold end processes, moisture on the bottle (e.g., from condensation) can adversely affect such systems, and some of the coatings, due to the long cure time of the moisture (condensation), can adversely affect the coating system. Many existing products exhibit poor or undesirable performance when applied to moist bottles or on cold bottles that become moist due to condensation. These include, but are not limited to, filling glass bottles or containers with cold products, which are typically cold liquids, such as bubble liquids, e.g., bubble water, soda, juices, beer, and the like. This poor performance is due to the fact that the condensed water on the exterior of the container causes further dilution of the masking product, causing 'rinsing off' of the applied coating. Such rinsing results in no coating remaining on the container surface.

Some coatings are undesirable because of their hygroscopic properties. These coatings become sticky and attract dust, which only serves to further degrade the appearance of the surface. The present disclosure is made against this background.

Purpose(s) to

Some objects of the present invention are to provide a composition to be applied on a recyclable container so as to face lift or mask a white reflective tape (scratch tape) that is present primarily during the filling process and typically after several shipments of the recyclable container at the container contact area.

It is another object of the present invention to provide a method for applying such compositions ('masking fluids or liquids') in order to restore the appearance of such containers, as the presence of the scratch tape detracts from the appearance of the container.

It is another object of the present invention to provide an efficient scratch or mar masking composition, especially in the case of fill conditions where the container is filled with a cold liquid and water condensation of moisture occurs at the surface of the container.

It is a further object to provide a sufficiently stable emulsion for administration but avoiding the inclusion of demulsifiers. It is a further object of the present invention to provide a composition that has good resistance to immersion in water and ice water, i.e., a composition that is not easily removed if the container in which it is located is immersed in water.

It is another object of the present invention to provide compositions that are non-slippery or greasy to the touch. Another object of the composition of the present invention is to facilitate removal during the bottle wash process with alkaline wash solutions.

It is another object of the present invention to provide a composition for masking scratches on the surface of containers that is non-toxic and meets the requirements generally recognized as safe for use in foods and beverages. It is another object of the present invention to provide a masking composition and method of application that does not damage the indicia on the exterior surface of the container.

It is another object of the present invention to provide masking compositions that are compatible with conveyor lubricants. That is, the compositions of the present invention neither build up or form residues on the conveyor nor affect the performance of the lubricant.

It is an additional object of the present invention to eliminate paraffinic oil from the mar masking composition or to provide a masking composition that is substantially free of paraffinic oil.

Disclosure of Invention

Compositions for masking scratches on the surface of a container are provided. The composition includes a carboxylic acid ester, a surfactant, and a fatty acid. In one example, the surfactant is an ethoxylated alcohol. In another embodiment, the fatty acid is a monounsaturated fatty acid. In another embodiment, the composition is suitable for masking scratches on the surface of containers including, but not limited to, glass bottles and PET bottles.

A composition for masking scratches on a glass or PET surface comprises about 50 wt% to about 99.9 wt% of a carboxylic acid ester, about 0.1 wt% to about 5 wt% of a surfactant, and about 0.1 wt% to about 20 wt% of a monounsaturated fatty acid. The scratch masking composition may be diluted with about 5 wt% to about 95 wt% water. In one example, the scratch masking composition is an aqueous emulsion.

In one example, a composition for masking scratches on a container surface (such as glass or PET) consists essentially of: from about 50% to about 99.9% by weight of a carboxylic acid ester, from about 0.1% to about 5% by weight of a surfactant and from about 0.1% to about 20% by weight of a monounsaturated fatty acid.

In one example, the composition consists of: from about 50% to about 99.9% by weight of a carboxylic acid ester, from about 0.1% to about 5% by weight of a surfactant and from about 0.1% to about 20% by weight of a monounsaturated fatty acid.

In one example, the masking composition is diluted with a dilution liquid (e.g., water). The diluted composition comprises from about 4 wt% to about 90 wt% of a carboxylic acid ester, from about 0.1 wt% to about 2 wt% of a surfactant, and from about 0.25 wt% to about 5 wt% of a monounsaturated fatty acid. In another embodiment, the diluted masking composition consists essentially of: from about 4% to about 90% by weight of a carboxylic acid ester, from about 0.1% to about 2.0% by weight of a surfactant and from about 0.1% to about 5% by weight of a monounsaturated fatty acid.

Methods of applying the compositions to containers for masking scratches are also provided. In one example, the method includes applying an undiluted or neat masking composition including a carboxylic acid ester, a surfactant, and a fatty acid to a cold glass or PET container. In one example, the method comprises preparing an emulsion of a carboxylic acid ester, a surfactant, and a fatty acid and diluting the emulsion with about 5 wt% to about 95 wt% water prior to applying the composition to a cold glass or PET container. In some embodiments, the surfactant comprises an ethoxylated alcohol and the fatty acid comprises a monounsaturated fatty acid.

In another embodiment, the method comprises applying to the container a composition comprising from about 50 wt% to about 99.9 wt% carboxylic acid ester, from about 0.1 wt% to about 5 wt% surfactant, and from about 0.1 wt% to about 20 wt% monounsaturated fatty acid.

In one example, the method comprises applying to a container a composition consisting essentially of: from about 50% to about 99.9% by weight of a carboxylic acid ester, from about 0.1% to about 5% by weight of a surfactant and from about 0.1% to about 20% by weight of a monounsaturated fatty acid. In yet another embodiment, the method comprises applying to the container a composition consisting of: from about 50% to about 99.9% by weight of a carboxylic acid ester, from about 0.1% to about 5% by weight of a surfactant and from about 0.1% to about 20% by weight of a monounsaturated fatty acid.

In one example, the method comprises applying to a container a diluted composition consisting essentially of: from about 4% to about 90% by weight of a carboxylic acid ester, from about 0.1% to about 2% by weight of a surfactant and from about 0.25% to about 5% by weight of a monounsaturated fatty acid. In yet another embodiment, the method of the invention comprises administering a composition consisting of: from about 4% to about 90% by weight of a carboxylic acid ester, from about 0.1% to about 2.0% by weight of a surfactant and from about 0.1% to about 5% by weight of a monounsaturated fatty acid.

Methods of applying the scratch masking composition to the container include spraying, dipping, flow coating, brushing, roll coating, sponge wiping, spraying, and curtain coating. In one example, the composition is sprayed onto the surface of the container through an energized or non-energized nozzle. Energized nozzles refer to nozzles that require some form of energy, such as high pressure (above the pressure of the nozzle itself), compressed air, or sonication to break the composition into fine droplets. In contrast, a non-energized nozzle refers to a nozzle that is capable of breaking up a composition into fine droplets using only the nozzle itself when operating at the desired operating parameters.

These and other aspects, advantages, and salient features of the present disclosure will become apparent from the following description and claims.

Detailed Description

As used herein, the term "cold" refers to a temperature below ambient, such as below about 20 ℃. By "cold" surface is meant any surface having a temperature lower than the ambient air temperature, which will thereby promote condensation of atmospheric moisture on the surface. One skilled in the art will recognize that if the ambient temperature is 23 ℃, condensation may occur on any surface colder than 23 ℃ depending on the relative humidity of the atmosphere. For the purposes of the present invention, "cold" refers to the temperature of any surface that is below ambient or ambient temperature, thereby possibly promoting the formation of condensation on the surface. "Cold" can also be defined as a temperature greater than 0 ℃ and up to about 5 ℃, freezing point to about 4.5 ℃ or minus to about 4.5 ℃.

As used herein, the term "phosphate-free" refers to a composition, mixture, or ingredient that does not contain a phosphate or phosphate-containing compound or to the absence of added phosphate or phosphate-containing compound. If the phosphate ester or phosphate-containing compound is present by contamination of the non-phosphate ester-containing composition, mixture, or ingredient, the amount of phosphate ester is less than about 0.5 wt%, less than about 0.1 wt%, or less than about 0.01 wt%.

As used herein, the term "phosphorus-free" refers to a composition, mixture, or ingredient that does not contain phosphorus or a phosphorus-containing compound, or to the absence of added phosphorus or a phosphorus-containing compound. If phosphorus or a phosphorus-containing compound is present by contaminating a non-phosphorus-containing composition, mixture, or ingredient, the amount of phosphorus is less than about 0.5 wt%, less than about 0.1 wt%, or less than about 0.01 wt%.

As used herein, the term "EDTA-free" refers to a composition, mixture, or ingredient that does not contain EDTA or to the absence of added EDTA. If EDTA is present through contamination of a composition, mixture, or ingredient that is free of EDTA, then the amount of EDTA is less than about 0.5 wt%, less than about 0.1 wt%, or less than about 0.01 wt%.

As used herein, the term "paraffin oil-free" refers to a composition, mixture, or ingredient that does not contain paraffin oil-containing compounds or to no paraffin oil added. If the paraffinic oil is present through contamination of a composition, mixture or component that is free of paraffinic oil, the amount of paraffinic oil is less than about 0.5 wt%, less than about 0.1 wt%, or less than about 0.01 wt%.

As used herein, weight percent (wt%), percent by weight, wt%, and the like are synonyms that refer to concentrations of substances in the form: the weight of the material is divided by the total weight of the composition and multiplied by 100.

As used herein, the term "about" modifying the amount of an ingredient employed in the disclosed compositions or in the disclosed methods refers to a composition that can be prepared, for example, by typical measurement and liquid handling procedures used in the real world for preparing use solutions; through the careless loss in these procedures; variations in the numerical quantities that occur through differences in the manufacture, source, or purity of the ingredients used to prepare the compositions or perform the methods, and the like. The term about also encompasses amounts that differ due to different equilibrium conditions of the composition resulting from a particular initial mixture. The claims include numerical equivalents of the claims whether or not modified by the term "about".

It should be noted that, as used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to a composition containing "a compound" includes mixtures of two or more compounds. It should also be noted that the term "or" is generally employed in its sense including "and/or" unless the context clearly dictates otherwise.

For the sake of brevity and conciseness, any range of values set forth in this specification encompasses all values within the stated range and should be understood as supporting claims reciting any subrange having endpoints which are real numbers within the stated range. By way of a hypothetical illustrative example, a range of 1 to 5 disclosed in this specification should be considered to support the claims to protect any one of the following ranges: 1-5; 1-4; 1-3; 1-2; 2-5; 2-4; 2-3; 3-5; 3-4; and 4-5.

The term "substantially free" can refer to the absence or near absence of any component of the disclosed composition. When referring to "substantially free," it is desirable that the components are not intentionally added to the disclosed compositions. The use of the term "substantially free of" a component allows for trace amounts of the component to be included in the disclosed composition as it is present in another component. However, it will be appreciated that when a composition is referred to as being "substantially free" of a component, only trace or minimal amounts of that component will be permitted. Furthermore, the term if a composition is said to be "substantially free" of a component, it is understood that it will not affect the efficacy of the composition if the component is present in trace or minimal amounts. It is to be understood that a composition may be substantially free of an ingredient if that ingredient is not explicitly included or if it may be included without being set forth herein. Likewise, the inclusion of a stated ingredient allows the stated exclusion thereof, thereby rendering the composition substantially free of the explicitly stated ingredient.

As used herein, with reference to a composition, the term "consisting essentially of …" refers to the listed ingredients and does not include additional ingredients that, if present, would affect the scratch masking ability of the composition. The term "consisting essentially of …" may also refer to a component of a composition. For example, a surfactant package may consist essentially of two or more surfactants, and such a surfactant package would not include any other ingredients that would affect the efficacy of the surfactant package (positively or negatively). As used herein, with reference to the method of application, the term "consisting essentially of …" refers to the listed steps and does not include additional steps (or ingredients, if included in the method) that would affect the ability of the composition to mask scratches on a surface if present.

The term "surfactant" or "surface active agent" refers to a chemical substance or additive that, when added to a liquid, changes the properties of the liquid at the surface.

Carboxylic acid esters

It has been surprisingly found that the appearance of scratches and gouges is diminished in the application of a combination of a surfactant (preferably a nonionic surfactant), a carboxylic acid ester and a monounsaturated fatty acid to the surface of a reusable container. The carboxylic acid esters included in the disclosed compositions can include a variety of carboxylic acid esters, such as esters, derivatives, or mixtures of monocarboxylic, dicarboxylic, or tricarboxylic acids that can be derived from the same or different alcohols and carboxylic acids. Mixtures of mono-aliphatic esters of carboxylic acids, mixtures of di-aliphatic esters of carboxylic acids, mixtures of tri-aliphatic esters of carboxylic acids, or mixtures of mono-, di-, and tri-aliphatic esters of carboxylic acids can be employed in the disclosed compositions. Examples of esters include mono-, di-or triesters of carboxylic acids derived from the following alcohols: n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, crotyl alcohol, isobutyl alcohol, isoamyl alcohol, and 2-ethylhexyl alcohol.

Esters are derived from the reaction of an alcohol with a carboxylic acid, where the latter may be organic or inorganic. Examples of esters of carboxylic acid esters suitable for use in preparing the compositions of the present invention include acetates, propionates, and butyrates, also referred to as formates, acetates, propionates, and butyrates using the IUPAC nomenclature.

Examples of suitable carboxylic acid esters are ethyl acetate derived from an alcohol (left) and from an acyl group of a carboxylic acid (right):

the chemical formula of the organic esters is generally taken to be RCO₂R 'form, wherein R and R' are the hydrocarbon moieties of carboxylic acids and alcohols, respectively.

In one example, the carboxylic acid ester is water insoluble. Examples of water-insoluble carboxylic acid esters suitable for use in the compositions of the present invention include, without limitation, butyl acetate, acetyltributyl citrate, isoamyl acetate, acetyl-tri-n-butyl citrate, n-propyl acetate, acetyltriethyl citrate, tri-n-butyl citrate, heptyl caprylate, acetyltri-n-butyl citrate, octyl caprylate, amyl valerate, 3-carboxy-3-hydroxypentane-1, 5-diacid, acetyltri-n-hexyl citrate, isoamyl caprylate, amyl butyrate, n-butyl tri-n-hexyl citrate, and combinations thereof.

In one example, the carboxylic acid ester is present in an amount of about 50 wt% to about 99.9 wt%, about 60 wt% to about 99 wt%, about 65 wt% to about 98 wt%, about 70 wt% to about 97 wt%, about 75 wt% to about 96 wt%, about 80 wt% to about 95 wt%, about 85 wt% to about 94 wt%, or about 91.5 wt% to about 94.5 wt%, based on the total weight of the pure masking composition.

When used, the masking composition may be diluted with water. In some embodiments, the carboxylic acid ester may be present from about 2 wt% to about 94.9 wt%, from about 3 wt% to about 90.2 wt%, from about 3.25 wt% to about 85.5 wt%, from about 3.5 wt% to about 80.7 wt%, from about 3.75 wt% to about 76 wt%, from about 4 wt% to about 71.2 wt%, from about 4.2 wt% to about 66.5 wt%, from about 4.5 wt% to about 61.7 wt%, from about 4.7 wt% to about 57 wt%, or from about 4.99 wt% to about 47.5 wt%, based on the total weight of the diluted masking composition.

Surface active agent

The composition includes one or more surfactants. Suitable surfactants include nonionic, cationic, anionic, amphoteric and zwitterionic surfactants and combinations thereof. In some embodiments, the surfactant is preferably a nonionic surfactant.

Exemplary nonionic surfactants include, but are not limited to, alcohol ethoxylates. Alcohol ethoxylates suitable for use in the compositions of the present invention can be derived from synthetic or natural fatty alcohols. Examples of synthetic alcohols for ethoxylation may be obtained from hydroformylation reactions that produce oxo alcohols or from oligomerization of ethylene under ziegler catalysts. Natural fatty alcohols are produced by reducing fatty acids. Oxo alcohol ethoxylates having straight or branched carbon chains with narrow to broad carbon chain length distributions may be used in the present invention. Examples of suitable alcohol ethoxylates include, but are not limited to, those commercially available from Huntsman (Huntsman)

L12-6, Emulsogen LA 3065, commercially available from Clariant,

n series, in Brij^TMOr Synperonic^TMThe group of poa-large (Croda's) ethoxylated fatty alcohols sold under the trade name Croda. Additional examples of nonionic surfactants suitable for use in the compositions of the present invention include, but are not limited to, alcohol ethoxylate propoxylates, alcohol propoxylate ethoxylate propoxylates, alcohol ethoxylate butoxylates, l available from BASF

Series, etc., or combinations thereof. The alcohol ethoxylate may be a linear or branched ethoxylate. In one example, a laureth alcohol ethoxylate is included in the composition, such as laureth-3, laureth-4, laureth-9, oleyl polyether-2, oleyl polyether-5, trideceth-3, or trideceth-5.

Other exemplary nonionic surfactants are listed below.

Block polyoxypropylene-polyoxyethylene polymeric compounds based on propylene glycol, ethylene glycol, glycerol, trimethylolpropane and ethylenediamine as initiator reactive hydrogen compounds such as: bifunctional block copolymers (available from BASF Corp.)

Product); and tetrafunctional block copolymers (available from basf corporation)

Products)

The condensation product of one mole of an alkylphenol in which the alkyl chain, having a straight or branched configuration or having a single or double alkyl composition, contains from about 8 to about 18 carbon atoms with from about 3 to about 50 moles of ethylene oxide. The alkyl group may be represented by, for example, a di-isobutylene group, a dipentyl group, a polymeric propylene group, an isooctyl group, a nonyl group, and a dinonyl group. These surfactants can be polyethylene oxide, polypropylene oxide and polybutylene oxide condensates of alkyl phenols. Commercially available examples include those available from Solvay s.a. of sovereil corporation

And available from the Dow Chemical Company

The condensation product of one mole of a saturated or unsaturated, straight or branched chain alcohol having from about 6 to about 24 carbon atoms with from about 3 to about 50 moles of ethylene oxide. The alcohol portion may consist of a mixture of alcohols within the carbon range delineated above, or it may consist of an alcohol having a specific number of carbon atoms within this range. Examples of commercially available materials include those available from Shell Chemical Co

And available from Sasol North America, Inc

The condensation product of one mole of a saturated or unsaturated, straight or branched chain carboxylic acid having from about 8 to about 18 carbon atoms with from about 6 to about 50 moles of ethylene oxide. The acid may be a mixture of acids within the carbon atom ranges defined hereinabove or the acid may be an acid having a specific number of carbon atoms within the ranges. Commercially available examples include those available from Lipo Chemicals, Inc

Alkanoic acid esters are formed by reaction with glycerides, glycerin, and polyhydric (sugar or sorbitan/sorbitol) alcohols. All of these ester moieties have one or more reactive hydrogen sites on their molecule that can undergo further acylation or ethylene oxide (alkoxide) addition to control the hydrophilicity of these materials.

In some embodiments, the composition comprises a low foaming nonionic surfactant. Exemplary low-foaming nonionic surfactants include:

reverse block copolymer which is a block copolymerThe inversion is mainly by adding ethylene oxide to ethylene glycol to provide a hydrophilic species of a given molecular weight, followed by propylene oxide to obtain a hydrophobic block on the outside (terminal) of the molecule. The hydrophobic portion of the molecule weighs from about 1,000 to about 3,100, with the intermediate hydrophilic species comprising from 10 wt% to about 80 wt% of the final molecule. Also included are difunctional reverse block copolymers (which may be)

R is commercially available from Pasteur) and a tetra-functional reverse block copolymer (which may be

R is commercially available from BASF corporation

A blocked nonionic surfactant modified by: with hydrophobic small molecules such as propylene oxide, butylene oxide, benzyl chloride, and the like; and short chain fatty acids, alcohols or alkyl halides containing from 1 to about 5 carbon atoms and mixtures thereof, to "cap" or "end cap" one or more terminal hydroxyl groups (of the polyfunctional moiety) to reduce foaming. Also included are reactants such as thionyl chloride, which converts the terminal hydroxyl group to a chloro group. Such modifications to the terminal hydroxyl groups can result in fully blocked, block-mixed, or fully-mixed nonionic surfactants.

Alkylphenoxypolyethoxyalkanols of U.S. patent No. 2,903,486 to Brown et al, issued 9, 8 1959, are represented by the formula:

wherein R is an alkyl group of 8 to 9 carbon atoms; a is an alkylene chain of 3 to 4 carbon atoms; n is an integer from 7 to 16; and m is an integer of 1 to 10.

The polyalkylene glycol condensates described in U.S. patent No. 3,048,548, issued to Martin et al on 8/7 of 1962, have alternating hydrophilic oxyethylene chains and hydrophobic oxypropylene chains, wherein the weight of the terminal hydrophobic chains, the weight of the intermediate hydrophobic units, and the weight of the linking hydrophilic units each account for about one-third of the condensate.

Defoaming nonionic surfactants disclosed in U.S. Pat. No. 3,382,178 issued to Lissant et al, 5/7/1968 and having the general formula Z [ (OR)_nOH]_zWherein Z is an oxyalkylatable material; r is a group derived from a basic oxide, which may be ethylene and propylene; n is an integer of, for example, 10 to 2,000 or more; and z is an integer determined by the number of reactive oxyalkylatable groups. Examples of commercially available defoaming or low-foaming nonionic surfactants include

And

all available from basf corporation.

The conjugated polyoxyalkylene compounds described in U.S. Pat. No. 2,677,700 to Jackson et al, 5/4/1954, correspond to the formula Y (C)₃H₆O)_n(C₂H₄O)_mH, wherein Y is the residue of an organic compound having about 1 to 6 carbon atoms and one reactive hydrogen atom; n has an average value of at least about 6.4 as determined by the hydroxyl number; and m is a value such that the oxyethylene moieties comprise about 10 to about 90 weight percent of the molecule.

A conjugated polyoxyalkylene compound described in U.S. Pat. No. 2,674,619 issued to Lundsted et al on 4/6/1954 and having the formula Y [ (C)₃H₆O_n(C₂H₄O)_mH]_xWherein Y is the residue of an organic compound having from about 2 to 6 carbon atoms and containing x reactive hydrogen atoms, wherein x has a value of at least about 2; n is a value such that the molecular weight of the polyoxypropylene hydrophobic matrix is at least about 900; and m is a value such that the oxyethylene content of the molecule is about 10 to about 90 weight percent. Compounds falling within the definition of Y include, for example, propylene glycol, glycerol, pentaerythritol, trimethylolpropane, ethylenediamine, and the like. The oxypropylene chain optionally but advantageously contains a small amount of ethylene oxide, and the oxyethylene chain also optionally but advantageously containsA small amount of propylene oxide.

The additional conjugated polyoxyalkylene surface active agent corresponds to the formula: p [ (C)₃H₆O)_n(C₂H₄O)_mH]_xWherein P is the residue of an organic compound having about 8 to 18 carbon atoms and containing x reactive hydrogen atoms, wherein x has a value of 1 or 2; n is a value such that the molecular weight of the polyoxyethylene moiety is at least about 44; and m is a value such that the oxypropylene content of the molecule is from about 10 wt% to about 90 wt%. In either case, the oxypropylene chains may optionally contain small amounts of ethylene oxide, and the oxyethylene chains may also optionally contain small amounts of propylene oxide.

Other conjugated polyoxyalkylene surfactants, sometimes described as long-term surfactants, correspond to the formula: p (C)₃H₆O)_n(C₂H₄O)_mH, wherein P is the residue of an organic compound having about 8 to 18 carbon atoms and containing x reactive hydrogen atoms, wherein x has a value of 1 or 2; n has a value of 1 to 20; and m has a value of 1 to 20. Examples are the LUTENSOL XL series from Pasteff.

The polyhydroxy fatty acid amide surfactant comprises a surfactant having the formula R²CONR¹Z, wherein: r¹Is H, C₁-C₄Hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, ethoxy, propoxy, or mixtures thereof; r²Is C₅-C₃₁A hydrocarbyl group, which may be linear; and Z is a polyhydroxy hydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyl groups directly attached to the chain or an alkoxylated derivative thereof (preferably ethoxylated or propoxylated). Z may be derived from a reducing sugar in a reductive amination reaction; such as a glycidyl moiety.

Alkyl ethoxylate condensation products of fatty alcohols with from about 0 to about 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol may be a linear or branched primary or secondary alkyl group and generally contains from 6 to 22 carbon atoms.

Ethoxylation C₆-C₁₈Fatty alcohols and C₆-C₁₈Mixing ethoxylated and propoxylated fatty alcohols. Suitable ethoxy groupsThe fatty alcohol includes C with ethoxylation degree of 3-50₁₀-C₁₈An ethoxylated fatty alcohol.

Nonionic alkyl polysaccharide surfactants include those disclosed in U.S. patent No. 4,565,647 to lleado, 21 st.1.1986. These surfactants include hydrophobic groups containing from about 6 to about 30 carbon atoms; and polysaccharides, such as polyglycoside hydrophilic groups containing from about 1.3 to about 10 saccharide units. Any reducing sugar containing 5 or 6 carbon atoms can be used, for example the glucosyl moiety can be replaced by glucose, galactose and galactosyl moieties. (optionally, a hydrophobic group is attached at 2, 3,4, etc. positions, thus resulting in a glucose or galactose as opposed to a glucoside or galactoside.) the intersugar linkage may for example be between one position of the additional sugar unit and the 2, 3,4 and/or 6 position on the preceding sugar unit. Similar functionality may be achieved by a glucamide surfactant (e.g., the GLUCOPURE product available from clariant).

The fatty acid amide surfactant comprises a surfactant having the formula R⁶CON(R⁷)₂Wherein R is⁶Is an alkyl group containing 7 to 21 carbon atoms; and each R⁷Independently of one another is hydrogen, C₁-C₄Alkyl radical, C₁-C₄Hydroxyalkyl or- (C)₂H₄O)_XH, wherein x is 1 to 3.

Another class of nonionic surfactants includes the class defined as alkoxylated amines or most particularly alcohol alkoxylated/aminated/alkoxylated surfactants. These nonionic surfactants can be represented at least in part by the general formula: r²⁰--(PO)_SN--(EO)_tH、R²⁰--(PO)_SN--(EO)_tH(EO)_tH and R²⁰--N(EO)_tH; wherein R is²⁰Alkyl, alkenyl or other aliphatic or alkyl-aryl groups of 8 to 20, preferably 12 to 14 carbon atoms, EO is oxyethylene, PO is oxypropylene, s is 1-20, preferably 2-5, t is 1-10, preferably 2-5, and u is 1-10, preferably 2-5.

Other variations of the scope of these compounds may be represented by the following alternative formulae: r²⁰--(PO)_v--N[(EO)_wH][(EO)_zH]Wherein R is²⁰Is an alkyl, alkenyl or other aliphatic or alkyl-aryl group of 8 to 20, preferably 12 to 14 carbon atoms, v is 1 to 20 (e.g. 1, 2, 3 or 4 (preferably 2)), and w and z are independently 1-10, preferably 2-5. These compounds are commercially represented by a series of products sold by Huntsman chemical industries as nonionic surfactants. One exemplary chemical of this class includes SURFONIC^TMPEA 25 amine alkoxylates.

The composition may further comprise a semi-polar nonionic surfactant. Examples of semi-polar nonionic surfactants include:

amine oxides are tertiary amine oxides corresponding to the general formula:

wherein the arrow is a conventional representation of a semipolar bond; and, R¹、R²And R³May be aliphatic, aromatic, heterocyclic, alicyclic, or combinations thereof. In general, for detergent related amine oxides, R¹An alkyl group of from about 8 to about 24 carbon atoms; r²And R³Is an alkyl or hydroxyalkyl group of 1 to 3 carbon atoms or mixtures thereof; r²And R³May be attached to each other, for example, through an oxygen atom or a nitrogen atom, to form a ring structure; r⁴Is a base or a hydroxyalkylene group containing 2 to 3 carbon atoms; and n ranges from 0 to about 20.

Suitable water-soluble amine oxide surfactants may be selected from coconut or tallow alkyl di- (lower alkyl) amine oxides, specific examples of which are dodecyl dimethyl amine oxide, tridecyl dimethyl amine oxide, tetradecyl dimethyl amine oxide, pentadecyl dimethyl amine oxide, hexadecyl dimethyl amine oxide, heptadecyl dimethyl amine oxide, octadecyl dimethyl amine oxide, dodecyl dipropyl amine oxide, tetradecyl dipropyl amine oxide, hexadecyl dipropyl amine oxide, tetradecyl dibutyl amine oxide, octadecyl dibutyl amine oxide, bis (2-hydroxyethyl) dodecyl amine oxide, bis (2-hydroxyethyl) -3-dodecyloxy-1-hydroxypropyl amine oxide, dimethyl- (2-hydroxydodecyl) amine oxide, 3,6, 9-trioctadecyl dimethyl amine oxide and 3-dodecyloxy-2-hydroxypropyl bis- (2-hydroxyethyl) amine oxide.

The semi-polar nonionic surfactant also includes a water-soluble phosphine oxide having the structure:

wherein the arrow is a conventional representation of a semipolar bond; r¹Is an alkyl, alkenyl or hydroxyalkyl moiety having a chain length in the range of from 10 to about 24 carbon atoms; and R is²And R³Each an alkyl moiety independently selected from alkyl or hydroxyalkyl groups containing from 1 to 3 carbon atoms. Examples of suitable phosphine oxides include dimethyldecyl phosphine oxide, dimethyltetradecyl phosphine oxide, methylethyltetradecyl phosphine oxide, dimethylhexadecyl phosphine oxide, diethyl-2-hydroxyoctyldecyl phosphine oxide, bis (2-hydroxyethyl) dodecyl phosphine oxide, and bis (hydroxymethyl) tetradecyl phosphine oxide.

Semi-polar nonionic surfactants also include water-soluble sulfoxide compounds having the structure:

wherein the arrow is a conventional representation of a semipolar bond; r¹Is an alkyl or hydroxyalkyl moiety having from about 8 to about 28 carbon atoms, from 0 to about 5 ether linkages, and from 0 to about 2 hydroxyl substituents; and R is²Is an alkyl moiety consisting of an alkyl group having 1 to 3 carbon atoms and a hydroxyalkyl group. Suitable examples of such sulfoxides include dodecyl methyl sulfoxide; 3-hydroxytridecyl methyl sulfoxide; 3-methoxytridecylmethyl sulfoxide; and 3-hydroxy-4-dodecyloxybutylmethylsulfoxide.

In some embodiments, one or more nonionic surfactants may be included in the scratch masking composition. Nonionic surfactant packages can be used to prepare the disclosed compositions.

Exemplary anionic surfactants include: carboxylic acids and salts thereof, such as alkanoic acids and alkanoates, ester carboxylic acids (e.g., alkyl succinates), ether carboxylic acids, and the like; phosphate esters and salts thereof; sulfonic acids and salts thereof, such as isethionates, alkylarylsulfonates, alkylsulfonates, ester sulfonates, sulfosuccinates; and sulfuric acid esters and salts thereof, such as alkyl ether sulfates, alkyl sulfates, and the like.

Anionic surfactants include those having a negative charge on the hydrophilic group, or surfactants in which the molecule is not charged unless the pH is raised to be electrically neutral or higher (e.g., carboxylic acids). Carboxylates, sulfonates, sulfates and phosphates are polar (hydrophilic) solubilizing groups found in anionic surfactants. Sodium, lithium and potassium in the cations (counterions) associated with these polar groups impart water solubility; ammonium and substituted ammonium ions provide water and oil solubility; and calcium, barium and magnesium promote oil solubility. The particular salt is suitably selected depending on the needs of the particular formulation.

Most of the large number of commercial anionic surfactants can be subdivided into five major chemical classes and additional subgroups as known to those skilled in the art and described in the Surfactant Encyclopedia, Cosmetics and Toiletries, volumes 104 (2)71-86 (1989). The first class includes acylamino acids (and salts), such as acylglutamates, acyl peptides, sarcosinates (e.g., N-acyl sarcosinates), taurate esters (e.g., fatty acid amides of N-acyl taurates and methyltaurates), and the like. The second class includes carboxylic acids (and salts), such as alkanoic acids (and alkanoates), ester carboxylic acids (e.g., alkyl succinates), ether carboxylic acids, and the like. The third class includes phosphate esters and salts thereof. The fourth class includes sulfonic acids (and salts), such as isethionates (e.g., acyl isethionates), alkylaryl sulfonates, alkylsulfonates, sulfosuccinates (e.g., monoesters and diesters of sulfosuccinate esters), and the like. The fifth class includes sulfates, such as alkyl ether sulfates, alkyl sulfates, and the like.

Exemplary anionic surfactants include the following:

linear and branched primary and secondary alkyl sulfates, alkyl ethoxy sulfates, fatty oil-based glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, C₅-C₁₇acyl-N- (C)₁-C₄Alkyl) and-N- (C)₁-C₂Hydroxyalkyl) reduced glucosamine sulfate, and sulfates of alkyl polysaccharides, such as alkyl polyglucoside sulfates (the nonionic non-sulfated compounds are described herein).

Ammonium and substituted ammonium (e.g. mono-, di-and triethanolamine) and alkali metal (e.g. sodium and potassium) salts of alkyl mononuclear aromatic sulfonates, such as alkyl benzene sulfonates containing from 5 to 18 carbon atoms in the alkyl group in the straight or branched chain, for example alkyl benzene sulfonates or salts of alkyl toluene, xylene, cumene and phenol sulfonates; alkyl naphthalene sulfonates, diamyl naphthalene sulfonates, and dinonyl naphthalene sulfonates and alkoxylated derivatives.

Anionic carboxylate surfactants (e.g., alkyl ethoxy carboxylates), alkyl polyethoxy polycarboxylate surfactants, and soaps (e.g., alkyl carboxylates). Second soap surfactants (e.g., alkyl carboxyl surfactants) include those that contain a carboxyl unit attached to a secondary carbon. The secondary carbon may be in the ring structure, for example, as in p-octylbenzoic acid, or as in alkyl-substituted cyclohexyl carboxylate. The second soap surfactant typically contains no ether linkages, no ester linkages and no hydroxyl groups. In addition, they generally lack nitrogen atoms in the head group (amphiphilic portion). Suitable secondary soap surfactants typically contain a total of 11 to 13 carbon atoms, although more carbon atoms (e.g., up to 16) may be present.

Other anionic surfactants include olefin sulfonates such as long chain olefin sulfonates, long chain hydroxyalkane sulfonates or mixtures of olefin sulfonates and hydroxyalkane sulfonates. Also included are alkyl sulfates, alkyl poly (ethyleneoxy) ether sulfates and aromatic poly (ethyleneoxy) sulfates such as the sulfates or condensation products of ethylene oxide and nonylphenol (typically having 1 to 6 ethylene oxide groups per molecule). Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids are present in or derived from tallow oil.

Exemplary cationic surfactants include amines, such as alkyl amines and amido amines. The composition may comprise a cationic surfactant selected from amino or other cationic surfactants. The amine groups include, for example, alkylamines and salts thereof, alkylimidazolines, ethoxylated amines, and quaternary ammonium compounds and salts thereof. Other cationic surfactants include sulfur (sulfonium) and phosphorus (phosphonium) based compounds similar to amine compounds.

Cationic surfactants generally refer to compounds containing at least one long carbon chain hydrophobic group and at least one positively charged nitrogen. The long carbon chain group may be attached directly to the nitrogen atom by simple substitution; or indirectly to the nitrogen atom via a bridging function in so-called interrupted alkylamines and amidoamines. Such functional groups may render the molecule more hydrophilic and/or more water dispersible, more readily soluble in water by the co-surfactant mixture, or render it soluble in water. To increase water solubility, additional primary, secondary or tertiary amino groups may be introduced; or the amino nitrogen may be quaternized with a low molecular weight alkyl group. In addition, the nitrogen may be a branched or straight chain moiety with varying degrees of unsaturation or part of a saturated or unsaturated heterocyclic ring. Furthermore, cationic surfactants may contain complex linkages with more than one cationic nitrogen atom.

Surfactant compounds classified as amine oxides, amphoteric surfactants, and zwitterionic surfactants are themselves typically cationic in solutions near neutral to acidic pH and may overlap with the surfactant classification. Polyoxyethylated cationic surfactants behave substantially like nonionic surfactants in alkaline solutions and similar to cationic surfactants in acidic solutions.

The simplest cationic amines, amine salts and quaternary ammonium compounds can be schematically drawn as:

wherein R represents a long alkyl chain, R ', R "and R'" can be either a long alkyl chain or a smaller alkyl or aryl group or hydrogen and X represents an anion.

Most of the large number of commercially available cationic surfactants can be subdivided into four main chemical classes and further subgroups, as known to the person skilled in the art and described in the encyclopedia of surfactants, "cosmetics and toiletries", volume 104 (2)86-96 (1989). The first class includes alkylamines and salts thereof. The second class includes alkyl imidazolines. The third class includes ethoxylated amines. The fourth class includes quaternary ammonium salts such as alkylbenzyldimethylammonium salts, alkylbenzene salts, heterocyclic ammonium salts, tetraalkylammonium salts, and the like. Cationic surfactants are known to have a variety of characteristics including detergency, antimicrobial efficacy, thickening or gelling in cooperation with other agents, and the like, in compositions at or below neutral pH.

Exemplary cationic surfactants include those having the formula R¹ _mR² _xY_LZ, wherein each R¹Is an organic group containing a linear or branched alkyl or alkenyl group, optionally substituted with up to three phenyl or hydroxy groups and optionally interrupted by up to four of the following structures:

or isomers or mixtures of these structures and contain from about 8 to 22 carbon atoms. R¹The radicals may additionally contain up to 12 ethoxy groups; m is a number from 1 to 3. Preferably, when m is 2, no more than one R is present in the molecule¹The group has 16 or more carbon atoms, or more than 12 carbon atoms when m is 3. Each R²Is an alkyl or hydroxyalkyl radical having from 1 to 4 carbon atoms or not more than one R in the molecule²In the case of benzyl, is benzyl, and x is a number from 0 to 11, preferably from 0 to 6. Any remaining carbon atom positions on the Y group are filled with hydrogen.

Y may be a group such as one of:

or mixtures thereof. Preferably, L is 1 or 2, wherein when L is 2, the Y group is selected from R having from 1 to 22 carbon atoms and two free carbon single bonds¹And R²The moieties of the analog (preferably alkylene or alkenylene) are spaced apart. Z is a water-soluble anion, such as a sulfate, methylsulfate, hydroxide or nitrate anion, particularly preferably a sulfate or methylsulfate anion, in a number such that the cationic component is electrically neutral.

Amphoteric and zwitterionic surfactants include derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium, or tertiary sulfonium compounds. The ammonium, phosphonium, or sulfonium compounds can be substituted with aliphatic substituents, such as alkyl, alkenyl, or hydroxyalkyl; alkylene or hydroxyalkylene; or a carboxylic, sulfonic, sulfuric, phosphonic or phosphoric acid group. Betaine and sulfobetaine surfactants are exemplary zwitterionic surfactants for use in the compositions of the present invention.

Zwitterionic surfactants can be considered as a subset of amphoteric surfactants. Zwitterionic surfactants can be described generally as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium, or tertiary sulfonium compounds. Typically, zwitterionic surfactants include positively charged quaternary ammonium ions, or in some cases, sulfonium or phosphonium ions, negatively charged carboxy groups, and alkyl groups. Zwitterions generally contain cationic and anionic groups, which ionize to almost the same degree in the isoelectric region of the molecule and which can produce strong "inner salt" attractions between positive-negative charge centers. Examples of such synthetic zwitterionic surfactants include derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radicals can be straight or branched chain, and wherein one of the aliphatic substituents contains from 8 to 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate. Betaine and sulfobetaine surfactants are exemplary zwitterionic surfactants.

These compounds have the general formula:

wherein R is¹An alkyl, alkenyl or hydroxyalkyl group containing from 8 to 18 carbon atoms having from 0 to 10 ethylene oxide moieties and from 0 to 1 glyceryl moiety; y is selected from the group consisting of nitrogen, phosphorus and sulfur atoms; r²Is an alkyl or monohydroxyalkyl group containing 1 to 3 carbon atoms; x is 1 when Y is a sulfur atom and x is 2 when Y is a nitrogen or phosphorus atom; r³Is an alkylene or hydroxyalkylene of 1 to 4 carbon atoms and Z is a group selected from the group consisting of carboxylate, sulfonate, sulfate, phosphonate and phosphate.

Examples of zwitterionic surfactants having the structure listed above include: 4- [ N, N-bis (2-hydroxyethyl) -N-octadecylammonium ] -butane-1-carboxylic acid salt; 5- [ S-3-hydroxypropyl-S-hexadecylthiocyano ] -3-hydroxypentane-1-sulfate; 3- [ P, P-diethyl-P-3, 6, 9-trioxacanetetraalkylphospho ] -2-hydroxypropan-1-phosphate; 3- [ N, N-dipropyl-N-3-dodecyloxy-2-hydroxypropyl-ammonio ] -propane-1-phosphonate; 3- (N, N-dimethyl-N-hexadecylammonium) -propane-1-sulfonate; 3- (N, N-dimethyl-N-hexadecylammonio) -2-hydroxy-propane-1-sulfonate; 4- [ N, N-bis (2 (2-hydroxyethyl) -N (2-hydroxydodecyl) ammonio ] -butane-1-carboxylate, 3- [ S-ethyl-S- (3-dodecyloxy-2-hydroxypropyl) dihydrothio ] -propane-1-phosphate, 3- [ P, P-dimethyl-P-dodecylphosphonium ] -propane-1-phosphonate, and S [ N, N-bis (3-hydroxypropyl) -N-hexadecylammonio ] -2-hydroxy-pentane-1-sulfate.

Zwitterionic surfactants include betaines and sulfobetaines of the general structure:

for example, cocamidopropyl betaine has the following structure:

and cocamidopropyl sulfobetaine has the following structure:

these surfactant betaines generally neither exhibit strong cationic or anionic character at the extremes of pH nor show a decrease in water solubility in their isoelectric range. Unlike "external" quaternary ammonium salts, betaines are compatible with anionic surfactants. Examples of suitable betaines include cocoacylamidopropyl dimethyl betaine; cetyl dimethyl betaine; c_12-14Acylamidopropyl betaine; c_8-14Acylamidohexyl diethylbetaine; 4-C_14-16Acylaminomethylaminodiethylammonium-1-carboxybutane; c_16-18Acylamidodimethylbetaine; c_12-16Acylamidopentane diethylbetaine; and C_12-16Acyl methyl amido dimethyl betaine.

The sulfobetaine comprises a compound having the formula (R)¹)₂N⁺R²SO^3-Wherein R is C₆-C₁₈A hydrocarbon radical, each R¹Is generally independently C₁-C₃Alkyl, e.g. methyl, and R²Is C₁-C₆Hydrocarbyl radicals, e.g. C₁-C₃Alkylene or hydroxyalkylene radicals。

Amphoteric surfactants contain both basic and acidic hydrophilic groups as well as organic hydrophobic groups. These ionic entities may be any of the anionic or cationic groups described herein for other types of surfactants. Basic nitrogen and acidic carboxylate groups are typical functional groups used as basic and acidic hydrophilic groups. In some surfactants, the sulfonate, sulfate, phosphonate, or phosphate groups provide a negative charge.

Amphoteric surfactants can be described generally as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radicals can be straight or branched chain and wherein one of the aliphatic substituents contains from 8 to 18 carbon atoms and one contains an anionic hydrotropic group, such as a carboxyl, sulfonate, sulfato, phosphato or phosphonyl group. Amphoteric surfactants are subdivided into two main classes, as known to the person skilled in the art and described in the encyclopedia of surfactants, "cosmetics and toiletries", Vol.104 (2)69-71 (1989). The first class includes acyl/dialkyl ethylenediamine derivatives (e.g., 2-alkyl hydroxyethyl imidazoline derivatives) and salts thereof. The second class includes N-alkyl amino acids and salts thereof. It is believed that some amphoteric surfactants may meet both classes.

Amphoteric surfactants can be synthesized by methods known to those of ordinary skill in the art. For example, 2-alkylhydroxyethylimidazolines are synthesized by condensation and ring closure of long chain carboxylic acids (or derivatives) with dialkylethylenediamine. Commercially available amphoteric surfactants undergo subsequent hydrolysis and ring-opening derivatization of the imidazoline ring by alkylation (e.g., with ethyl acetate). During alkylation, one or both carboxy-alkyl groups react with different alkylating agents to form tertiary amines and ether linkages, yielding different tertiary amines.

Exemplary commercially available imidazoline derived amphoteric surfactants include: cocoamphopropionate, cocoamphocarboxypropionate, cocoamphoglycinate, cocoamphocarboxyglycinate, cocoamphopropyl sulfonate, and cocoamphocarboxypropionic acid. Preferred amphoteric carboxylic acids may be derived from fatty imidazolines, wherein the dicarboxylic acid functionality of the amphoteric dicarboxylic acids is diacetic acid and/or dipropionic acid. The carboxy methylated compounds (glycinates) described herein are often referred to as betaines.

Long chain N-alkyl amino acids are accessible by RNH₂(wherein R is C₈-C₁₈Straight or branched chain alkyl), fatty amines with halogenated carboxylic acids. Alkylation of the primary amino group of an amino acid produces secondary and tertiary amines. The alkyl substituent may have additional amino groups providing more than one reactive nitrogen center. Most commercially available N-alkylamine acids are alkyl derivatives of beta-alanine or beta-N (2-carboxyethyl) alanine. Examples of commercially available N-alkyl amino acid ampholytes include alkyl beta-amino dipropionate, RN (C)₂H₄COOM)₂And RNHC₂H₄And (4) COOM. In these, R is preferably an acyclic hydrophobic group containing 8 to 18 carbon atoms, and M is a cation that neutralizes the charge of the anion.

Preferred amphoteric surfactants include those derived from coconut products such as coconut oil or coconut fatty acids. More preferably, these coconut derived surfactants include an ethylenediamine moiety, an alkanolamide moiety, an amino acid moiety, preferably glycine, or a combination thereof as part of their structure; and aliphatic substituents of about 8 to 18, preferably 12, carbon atoms. Such surfactants may also be considered to be alkyl amphodicarboxylic acids. Disodium cocoamphodipropionate is one of the most preferred amphoteric surfactants and is available under the trade name MIRANOL^TMFBS is commercially available from suwei ltd. Another most preferred coconut derived amphoteric surfactant (chemical name: disodium cocoamphodiacetate) is sold under the trade name MIRANOL^TMC2M-SF Conc, also from Suwei Inc.

The amount of surfactant may be from about 0.01 wt% to about 7.0 wt%, from about 0.05 wt% to about 5 wt%, from about 0.1 wt% to about 4.0 wt%, from about 0.5 wt% to about 3.5 wt%, from about 1 wt% to about 3 wt%, or from about 1.5 wt% to about 2.5 wt%, based on the total weight of the neat masking composition.

When used, the masking composition is diluted with water in one example. In some embodiments, the surfactant may be present from about 0.0005 wt% to about 6.65 wt%, from about 0.0025 wt% to about 4.75 wt%, from about 0.075 wt% to about 3.5 wt%, from about 0.15 wt% to about 2.85 wt%, from about 0.25 wt% to about 2.25 wt%, or from about 0.35 wt% to about 1.42 wt%, based on the total weight of the diluted masking composition.

Monounsaturated fatty acid

The composition includes at least one monounsaturated fatty acid distinguishable from the surfactant. Suitable monounsaturated fatty acids include, but are not limited to, monounsaturated fatty acids such as myristoleic acid, palmitoleic acid, hexadecenoic acid (sapienic acid), oleic acid, elaidic acid, vaccenic acid, linoleic acid, elaidic acid, alpha-linolenic acid, eicosatetraenoic acid, eicosapentaenoic acid, erucic acid, and docosahexaenoic acid, and combinations thereof. Examples of suitable saturated fatty acids include butyric, capric, caproic, caprylic, capric, lauric, myristic, palmitic and stearic acids, and combinations thereof. In one example, the fatty acids are selected so as not to impart an unpleasant odor to the composition.

With respect to the amount of fatty acid, in some aspects, the amount can be about 0.5 wt% to about 35.0 wt%, about 1 wt% to about 30 wt%, about 1.5 wt% to about 25 wt%, about 2 wt% to about 20 wt%, about 2.5 wt% to about 15 wt%, or about 3 wt% to about 10 wt%, based on the total weight of the pure masking composition.

When used, the masking composition is diluted with water in one example. In some embodiments, the fatty acid may be present from about 0.005 wt% to about 33.25 wt%, from about 0.075 wt% to about 19 wt%, from about 0.125 wt% to about 12 wt%, from about 0.5 wt% to about 9.5 wt%, from about 1 wt% to about 8 wt%, or from about 1.75 wt% to about 5 wt%, based on the total weight of the diluted masking composition.

The following table includes exemplary ranges for each ingredient in the pure compositions.

The following table includes exemplary ranges for each ingredient in the diluted composition.

Optional materials

In addition to the carboxylic acid ester, surfactant, and monounsaturated fatty acid, the disclosed compositions can include other optional materials. Exemplary materials include, but are not limited to, rheology modifiers, lubricants, antimicrobial agents, fluorescent tracers, and combinations thereof.

A rheology modifier.The composition may include an optional rheology modifier. The rheology modifier can increase the viscosity of the composition, increase the particle size of the composition when it is sprayed on a container, help improve the stability of the emulsion, and provide vertical adhesion of the composition on the surface of the container. When used in a masking composition, the rheology modifier may also help form a film on the container and improve the water repellency characteristics of the composition. The rheology modifier may be provided as a plastic-like use composition, meaning that it maintains a high viscosity when left undisturbed, substantially but reversibly decreases in viscosity when sheared, and recovers the high viscosity after shearing. In the disclosed application, the viscosity of the composition may be high when the composition is a concentrate or diluted with water, may become low when the composition is sprayed through a nozzle or other dispensing device, and may resume increasing when the composition is located on the surface of a container. The rheology modifier prevents the composition from dripping, running, sagging, or moving down the container due to gravity while on the surface of the container. Exemplary rheology modifiers include natural or synthetic polymers, gums, or clays. Specific examples include carboxylated vinyl polymers such as polyacrylic acid and sodium salts thereof, polyacrylamide thickeners, cross-linked polyacrylates, xanthan gum compositions, sodium alginate and alginate jelly products, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, natural resins such as Colofonia, pine and copal, shellac, oils derived from oilseeds, plants and animals, and derivatives and combinations thereof. Commercially available cellulose product packIncluding those sold under the names METHOCEL and ETHOCEL (e.g., METHOCEL MX, METHOCEL E19, ETH STD 45, ETHOCEL STD100) by the dow chemical company or under the name KLUCEL by asia, the rheology modifier may be present from about 0.2 wt% to about 15 wt%, from about 0.3 wt% to about 10 wt%, or from about 0.5 wt% to about 5 wt%.

And (3) a lubricant.The composition may optionally include a lubricant to improve movement of the container during processing (including bottling and packaging stages), reduce friction of the bottle with any surfaces it encounters during processing, and reduce additional scratches and scratches. Exemplary lubricants include (but are not limited to): synthetic waxes, such as Cerasperse 174, Cerasperse 321BGW, and Cerasperse 174; polytetrafluoroethylene (PTFE); PTFE mixed in refined linseed oil; composites of PTFE and wax, such as Cerasperse 321 BG; polysiloxanes, such as SILIKOFLUAL NON-STICK 60; polysiloxane polymers, copolymers and derivatives, such as TEGO Glide 432 and TEGO Glide A115; and derivatives and combinations thereof. The lubricant may be present in the composition from about 0.5 wt% to about 25 wt%, from about 1 wt% to about 20 wt%, from about 2 wt% to about 15 wt%, or from about 3 wt% to about 10 wt%.

An antimicrobial agent.The composition may optionally include an antimicrobial agent to slow or reduce the growth of organisms in the composition. Exemplary antimicrobial agents include phenols (including halogenated and nitrophenols) and substituted bisphenols such as 4-hexylresorcinol, 2-benzyl-4-chlorophenol, and 2,4,4 '-trichloro-2' -hydroxydiphenyl ether, organic and inorganic acids such as citric acid and ascorbic acid and esters and salts thereof, such as dehydroacetic acid, peroxycarboxylic acids, peroxyacetic acid, methylparaben, cationic agents such as aromatic or linear quaternary ammonium compounds, aldehydes such as glutaraldehyde, isothiazolinone compounds such as 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one, fatty amine compounds such as oleyldiaminopropane, cocoalkyldiaminopropane and lauryldimethylamine, and halogens including iodine and chlorine compounds. The antimicrobial agent may be present in the composition in an amount sufficient to provide the desired antimicrobial properties or from 0 wt% to about 20 wt%, or from about 0.5 wt% to about 10 wt%.

The composition may optionally include a fluorescent agentDyes to trace and quantify the composition. Exemplary tracers include by name

Or 3D

Those sold by Nalco (Nalco) inc.

Process for preparing masking compositions

The masking composition is prepared by combining a carboxylic acid ester and a fatty acid. A surfactant is then added to the carboxylic acid ester and fatty acid combination, and the resulting combination is stirred until homogenization is complete. In another embodiment, a reverse process is used to prepare the combination. That is, the surfactant and the carboxylic acid ester are first combined, and then the fatty acid is added to the surfactant and carboxylic acid ester combination. The resulting composition was stirred until homogenization was complete.

Dilution of

The composition is provided neat or as a concentrate, which can be diluted with a dilution liquid to a use solution. Such dilution liquid may be water, an alcohol, such as isopropanol or ethanol, glycerol, monoethylene glycol and monopropylene glycol, or a combination thereof. In some embodiments, paraffinic oil (e.g., mineral oil) is not used as the dilution liquid. Likewise, in certain embodiments, the composition is substantially free or free of mineral oil.

In one example, the composition is applied undiluted or neat to the container surface. In other embodiments, the composition is diluted with water prior to application to the surface of the container. Such dilution may be performed at the food facility prior to application to the container. In one example, the neat masking composition is diluted with water. Such water may be tap water or deionized or distilled water. Since tap water is the cheapest and most widely available, the composition can be diluted with tap water. The dilution water may have between about 0 and about 350ppm CaCO 3. If the hardness of the dilution water is high (above about 350ppm CaCO3), then the use of water softening equipment may be convenient.

Diluting the neat masking composition with a dilution liquid (e.g., water) is between about 5 wt% and about 98 wt% water, between about 20 wt% and about 95 wt% water, between about 40 wt% and about 93 wt% water, between about 50 wt% and about 90 wt% water, and between about 60 wt% and about 88 wt% water. The masking composition is diluted with water at a dilution ratio of between about 1:2 to about 1: 90.

Method of using masking compositions

No special equipment is required for applying the composition to the container surface; it is intended that any and all known devices in the art facilitate the preparation, use, and methods of the present invention. The composition may be applied before or after filling the container. The container is filled and capped according to known methods. In one example, the container is glass or PET and the container is filled with a cold liquid. Filling the container with a cold liquid causes the temperature of the container to decrease, thereby allowing potential moisture in the air to condense on the container surface. In one example, the scratch masking composition is applied after the container is filled and closed. In another embodiment, the scratch masking composition is applied prior to filling the container.

As demonstrated by the examples, the efficacy of the scratch masking composition is not adversely affected by condensation that may be present on the outer surface of the glass container due to the temperature differences between the container, the fill liquid, and/or the external temperature and the relative humidity of the environment.

Marking may be performed before or after applying the scratch masking composition. The step of applying the scratch masking composition may be the last step before rewashing, refilling, and the marked glass container is again marketed and sold to the customer.

The application equipment may generally include mixing and storage vessels, pumps, delivery and feed lines, spray equipment, and control and monitoring equipment. In one example, an apparatus includes one or more mixing vessels; a dosing and circulating pump; a mixing unit (which may be the pump itself); a circulation pipe; application devices, such as sponges, brushes, sprayers, spray nozzles; and the like. If applied via spray coating, the composition may be applied through energized or non-energized nozzles. Other methods or devices for applying the masking composition to the container are contemplated, including via dipping, brushing, rolling, flow coating, and curtain coating.

In one example, the composition is stored in a container connected to the valve via a plastic tube. A separate water line is also connected to the valve. The water and composition are combined at the valve and flow into a stainless steel conduit (e.g., a static mixer) where the water and composition mix as a result of the fluid flowing through the conduit. After mixing with water in the pipe, the composition was sprayed onto the bottle via a nozzle.

In one example, the container is moved relative to the applicator and the coating liquid is applied to the exterior of the container at the same time. In one example, the spray device is operated continuously. This means that the glass container is continuously transported through the coating station by means of the conveyor line, wherein the spraying device is continuously operated to shower the outside of the glass container with coating liquid. However, there are alternative routes in which the applicator operates discontinuously and the coating liquid is applied only stepwise or upon recognition of the presence of the glass container at the coating station. This alternative method saves a considerable amount of coating liquid, since the coating liquid is only applied to the glass containers actually present at the coating station.

In one example, the composition is an emulsion, specifically an oil-in-water emulsion. However, it is also possible to use equilibrium solutions of liquids, preferably water-based solutions of liquids. The emulsions (particularly oil-in-water emulsions) are balanced to remain sufficiently stable for administration. As discussed, water is the dilution liquid. In one example, the coating liquid is fed to the applicator via at least one feed line. The common feed line for the coating liquid additionally helps to allow even distribution of the coating liquid onto the exterior of the glass container. The coating composition may be diluted in situ or at a separate location.

The apparatus may also include a controller for monitoring application of the scratch masking composition. The controller can be, for example, an optical sensor for detecting the presence or absence of a container in front of the applicator, and/or detecting the presence and number of scratched strips or scratches, such that a minimum amount of paint is applied to the container. According to one aspect, the controller is monitored via a computer that can interact with the dosing pump and the applicator. The apparatus may further comprise the use of air to distribute and dry the composition. Examples of mixing and application devices are presented in WO2005/049219, which is incorporated herein by reference for all purposes.

In one example, the coating composition and the dilution liquid are stored separately and fed to a common feed line. The neat coating composition and the dilution liquid can be thoroughly mixed by mixing prior to or within the common feed line. In one example, mixing is accomplished with a mixing device without moving parts, such as a mixing chamber, e.g., a swirl chamber, a mixing tank, etc., known from other applications, such as oil/gasoline mixing stations. A longitudinally extending mixing device having mixing vanes and/or mixing baffles within the liquid stream may be used such that the mixture of pure coating composition and dilution liquid is continuously converted to an emulsion while flowing through the mixing device.

Static mixing devices are suitable for use in the process of the present invention and the diluted coating composition remains sufficiently stable for application.

The type of container in which the composition of the invention and the method of the invention are employed is generally a reusable or recyclable container. Such containers are generally bottles and consist of PET or glass. A common type of returnable container to which the method of the invention is applied is a glass bottle, such as a beer bottle.

The invention is illustrated in more detail in the following non-limiting examples.

Examples

A scratch masking composition having the formulation provided in table 1 was prepared:

TABLE 1

Formulation 2C is a comparative formulation in that it includes a water-soluble ester. Formulation 6C is a comparative formulation in that it includes mineral oil.

Example 1 appearance after application and drying

A desirable feature of the scratch masking composition is to improve the optical appearance of the container for the customer. The optical appearance of the container was evaluated to determine the concentration range of the masking composition and the amount of the composition applied to the container.

The test method comprises the following steps:the scratched glass 0.33L bottles were weighed and then cooled to 4 ℃. The formulations provided in table 1 were diluted with 5 wt% water, 75 wt% water and 90 wt% water. Each concentration was applied separately to the surface of the vial using a non-energized nozzle to a cold vial having condensation on its surface. The bottles were then allowed to dry naturally at room temperature. Once dry, the bottle appearance was visually assessed. The results are provided in table 2.

TABLE 2

If qualified, the scratch covering is more than 90 percent.

Failure-surface retention scratch covers less than 90% of the scratches.

Generally, a range of 10-80mg of solution per vial is suitable for each vial. The results show that all bottles were covered by the emulsion of the invention. Table 3 shows the results of applying formulation 3 to ten bottles at different dilutions.

Table 3:

example 2 feeling after application and drying

Once applied to the glass bottle, a thin film of masking composition remains on the bottle. Ideally, there is no apparent "fingerprint" on the bottle.

The test method comprises the following steps:glass 0.33L bottles were cleaned, cooled and treated as provided in example 1. Once dry, touch the bottle with a clean finger. The intensity of the fingerprint on the vial is evaluated to see when the fingerprint has disappeared. If fingerprint lingering is not desired. The bottles were also tested for greasy or sticky feel. Table 4 knots providing fingerprint touch testFruit, and table 5 results of sensory testing:

table 4:

qualified as no fingerprint

Unqualified or existing fingerprint

TABLE 5

Qualified that the surface is not sticky or slippery

Unqualified product with greasy surface

Example 3 persistence of masking formulations

Once applied to the glass bottles, the scratch masking composition has a shelf life. Ideally, the masking composition should remain on the container and not disappear during the shelf life.

The test method comprises the following steps: glass 0.33L bottles were cleaned, cooled and treated as provided in example 1. Once dry, the bottle was immersed in a water bath at 30 ℃ for 72 hours. The bottles were checked every 12 hours to see if the coating remained on the bottles. The results are provided in table 6:

table 6:

the coating remained on the bottle for 72 hours

Failure-proof removal of the coating is demonstrated by scratch reproduction.

Example 4 Ice Water resistance

The masking composition should remain on the surface even when submerged in ice water.

The test method comprises the following steps: glass 0.33L bottles were cleaned, cooled and treated as provided in example 1. Once dry, the bottle was immersed in an ice bath for 72 hours. After 72 hours, the bottle was taken out and allowed to air dry at room temperature, and then the appearance of the scratch was visually checked. The results are shown in table 7 below:

table 7:

the coating remained on the bottle for 72 hours

Failure is the removal of the coating and the scratch reappears.

Example 5 durability of masking formulation to condensed Water

If the treated bottles are taken from refrigeration and stored at room temperature, condensation occurs on the bottle surface. After a period of time, the condensed water dries. Such condensation and drying should not have a substantial effect on the presence of the masking agent. This example was conducted to test the durability of the formulation after condensation and drying had occurred.

The test method comprises the following steps: glass 0.33L bottles were cleaned, cooled and treated as provided in example 1. Once dry, the bottle was placed in a refrigerator at 5 ℃ for 72 hours. The bottle was then removed from the refrigerator and stored at room temperature to generate condensed water on the bottle. The bottles were then stored at room temperature to allow the condensation to dry naturally. The bottles were visually evaluated to see if the coating remained and the results are provided in table 8 below. It should be noted that whether the coating remains on the surface is easily determined by whether the scratch returns.

Table 8:

pass-the coating remained on the bottle for 72 hours after water condensed.

Failure is no coating remaining and scratches reappear.

The test results show that for formulations 1, 3,4 and 5, the masking agent remained on the container surface.

Example 6 compatibility with Lubricant

Since the masking composition is applied during the production process when the conveyor lubricant is used, a defined amount of masking composition must be mixed with the conveyor lubricant. For this purpose, the coating composition of the present invention should not affect the lubrication of the conveyor or container. Likewise, no accumulation of residues of the lubricant, masking composition, or combination thereof should occur on the conveyor belt.

The test method comprises the following steps: the masking composition use (dilution) solution and conveyor lubricant were mixed in different ratios. The use of the solution was observed to see if the composition separated or if precipitation occurred. After applying the composition to a glass bottle as prepared according to example 1, the coefficient of friction was measured. The results are provided in table 9 below.

TABLE 9

The results demonstrate that formulations 1-5 are compatible with lubricants. When formulation 6 was used in the presence of a lubricant, the coefficient of friction was still low but black spots formed.

The present invention should not be considered limited to the particular examples described above, but rather should be understood to cover all aspects of the invention as fairly set out in the attached claims. Various modifications and equivalent processes of the present invention may be applicable as will be apparent to those skilled in the art upon review of the present specification.

Claims (14)

1. A composition for masking scratches on containers comprising a citrate ester or acetate ester, an ethoxylated alcohol surfactant and 0.5 to 20 wt% of a monounsaturated fatty acid, based on the total weight of the pure masking composition.

2. The composition of claim 1, wherein the monounsaturated fatty acid is cis-9-octadecenoic acid.

3. The composition of claim 1 or 2, comprising:

50-98 wt% of a citrate ester or an acetate ester;

0.1-5 wt% of an ethoxylated alcohol surfactant; and

0.5 to 20 wt% monounsaturated fatty acid, based on the total weight of the pure masking composition.

4. The composition of claim 1 or 2, which is diluted with water.

5. The composition of claim 1 or 2, wherein the composition is an aqueous emulsion.

6. The composition of claim 1 or 2, wherein the container is glass or plastic.

7. The composition of claim 6, wherein the container is glass.

8. The composition of claim 1 or 2, wherein the composition is free of paraffin oil.

9. A method of applying the composition of any one of claims 1-8 to a container for masking scratches comprising:

diluting said composition with 5-95 wt% water; and

the diluted composition is applied to a container.

10. The method of claim 9, wherein the composition is applied by spraying, dipping, brushing, rolling, flow coating, sponge wiping, spraying, or curtain coating.

11. The method of claim 9 or 10, wherein the container is glass or plastic.

12. The method of claim 11, wherein the container is glass.

13. The method of claim 9 or 10, wherein the temperature of the container surface is less than 20 ℃.

14. The method of claim 9 or 10, wherein the composition is free of paraffin oil.